Production of 2, 2-bis(oxyaryl)propane compounds



" PRODUCTION or 2,2-BIS(XYARYL)PROPANE' COMPOUNDS Joseph P. Henry, Kanawha, W. Va'., assignor to Union Carbide Corporation, a corporation of New York No Drawing. Application February 28, 1956 Serial No. 568,190

21 Claims. (Cl. 260- 613) invention relates to' the production of 2,2-bis (oxyary1)propane compounds. More particularly, the invention relates to the production of 2,2-bis(oxyaryl)propane compounds by the reaction of an oxyaryl compound, such as phenol, ortho-cr'esol, anisole, ortho-methyl anisole, and like compounds with an acyclic 0 H, hydrocarbon.

Heretofore, one of the processes for making 2,2-bis- (oxyaryl)prop-ane compounds, such as 2,2-bis(4-hydroxyphenyl)propane, has been by the condensation of an oxyaryl compound, such as phenol, with acetone in the presence of acidic condensation agents, such as sulfuric acid and hydrogen chloride. Water, which is a co-prodnet of the reaction, adversely affects the rate of. formation of the 2,2-bis(oxyaryl )propane. As a result, extended reaction periods are necessary for good yields unless expensive dehydration steps are employed. In order to avoid the undesirable features of the acetone process, it has more recently been proposed to employ a saturated dihalide such as 2,2-dichloropropane or an. unsaturated monohalide such as 2-chloropropene or a bis(organomercapto) methane instead of acetone as a co-reactant with the phenol. But these processes are also characterized by a number of undesirable features such as low yields, poor product quality, undesirable resinification and by-product formation, and in some instances by long reaction periods and extensive methods for the recovery of the 2,2-bisphenolicpropane.

I' have discovered that a 2,2-bis(oxyaryl)propane is produced by admixing and reacting an oxyaryl compound with an acyclic C H hydrocarbon in the presence of an acidic condensing agent, according to the following scheme:

condensingagent wherein R and R are hydrogen or lower alkyl groups.

The oxyaryl reactants useful in the process of this in-* ventionare those corresponding. to the general formula' where R and R can be hydrogen or a lower alkyl group, such. as methyl, ethyl, propyl, and the like, with .R and R being either the same or different.

I have further discovered that alkyl substitution on the benzene ring should be only in the ortho position with respect to the oxy group. Alkyl substitution in the meta position of the benzene ring, I have found, produces spirohydridene and spirochroman structures, with very little or no yield of the desired meta-alkyl substituted his(fruq(aryl)- propane compound.

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Among. the oxyaryl compounds which have been found particularly useful in practicing the process of this invention are phenol, anisol, ortho-cresol, and ortho-methyl ani'sole. Especially good yields of 2,2-bis(4-hydroxyphenyl) propane are achieved using phenol as the oxyariyl reactant.

The acyclic C H hydrocarbons found suitable for use in producing the 2,2-bis(oxyaryl) propanes according to the process of this invention are propadiene (allene, CH =O=CH and propyne (methyl acetylene and mixtures thereof. These C ll hydrocarbons exist in many plant streams of cracked parafins, and in propanepropylene and olefin gas streams and are easily removed from the main gas stream by known means, such as by sity of separating and purifying individual propadiene or propync fractions prior to the reaction with the oxyaryl compound. The reaction of the propadiene or propyne or mixtures thereof is not inhibited by the presence of inert gaseous diluents for instance saturated parafins as methane, ethane, and. propane; and also nitrogen, argon, neon, and the like. It is not necessary that such inert materials when present, he removed from the 0 H, stream. In somecases it may be desirable to add such inert diluents as an aid in controlling the reaction temperature and rate of addition of the C H reactants.

The amounts of reactants in this process are not narrowly critical. In practice, however, it is desirable to employ an excess of the oxyaryl reactant over the stoichiometric amount, and preferably in excess of two moles of the oxyaryl reactant per mole of the C l-l hydrocarbon.

According to my experience, best yields of the 2,2-bis (oxyaryljpropane are obtained when using about five to seven moles of the oxyaryl reactant per mole of the C H reactant.

The acidic condensation agents which I have found to be useful include the Friedel-Crafts type such asithe halides of boron, aluminum, zinc, iron, and tin, and the mineral acids, such as sulfuric acid, phenol sulfonic acid, and hydrogen fluoride. The Friedel-Crafts condensing agents are preferred for best yields, and boron trifluoride especially preferred when using phenol as the oxyaryl reactant.

Phenol is known to form an insoluble complex, how= ever, in contact with aluminum chloride which inactivotes the aluminum chloride to such a degree that it fails to promote the reaction of the 0 1-1 hydrocarbon. Because of this reason, they should not be employed together. However, in the process of this invention 1' have foundaluminurrr chloride-to be a useful condensing agent when employed. with oxyaryl compounds other than phenol and cresol. If desired, mixtures of two or more acidic condensing agents can be employed.

I have found it preferable to employ the acidic condensing agents in amounts from about 1 to about 5 parts per parts by weight of. the oxyaryl compound used. Greater or lesser amounts can also be used. It is also preferred thatthe acidic condensingv agents and the reactants be substantially free of water as the presence of water adversely affectsthe rate of formation of the desired 2,2-bis(oxyaryl)propane compounds. Since water is not a productof this reaction, substantially anhydrous reaction conditions can be maintained by drying thereactants and condensing agent before use. However, it is not a critical requirement of my process that anhydrous conditions must be maintained, for the presence of a small amount of water in the acidic condensing agentor reactants can be tolerated. Boron trifiuoride monohydrate' vcan, if desired, be washed with chloroform or recrystal (BF -H for instance, will act as a condensing agent i.

but will result in a slower rateof reaction than when anhydrous boron trifiuoride is used.

I The reaction of the oxyarylcompound andtheCbH; hydrocarhonproceeds at moderate temperatures, such as those within the range of about 0 C. to about 100 C., with temperatures within the range of 30 C. to about 60 C. being preferred. According to my experience, the'yields are low in reactions carried out at less than 0 C. When using the normally solid oxyaryl compounds, as phenol and ortho-cresol, it is preferred that the temperature be above about 40 C. or at least suflicient to provide for liquid phase reaction conditions. Temperatures above about 100 C. have been found not to be too desirable because of the possibility of side reactions and decomposition of the product which can be encountered, with a consequent reduction in yield of the desired product.

Contact time of the reactants is not critical in my process. .In carrying out my process in a batchwise manner, contact time can range from about 15 minutes to hours or more, depending upon the selected temperature and rate of addition of the C H reactant. In a continuous or semi-continuous process, the actual contact or reaction time might be much shorter. Subatmospheric or superatmospheric pressures can also be employed, but atmospheric pressures are most convenient.

The 2,2-bis(oxyaryl)propane compounds prepared in accordance with the process of this invention can be recovered from the reaction mixture by conventional means, such as by distillation, crystallization, and extraction operations. The preferred methods are by distilling the reaction mixture under reduced pressures after the acidic agent is removed, to recover the product as the distillation residue, or else by removing the acidic condensing agent by diluting the reaction mixture with a mixture of cold water and ice or a mixture of ice and dilute hydrochloric acid and recovering the organic products. However, the method is not critcial, and any method occurring to those skilled in the art, chemically or otherwise, of removing the catalyst or product can be used.

When phenol is employed as a reactant, the 2,2-bis(4- hydroxyphenyl)propane thus produced is easily removed from the reaction mixture by crystallization of a complex formed between phenol and 2,2-bis(4-hydroxyphenyl)propane at a temperature below about 90 C. The crystalline complex is easily removed from the reaction mixture by filtration. The complex can be decomposed by the application of heat as in distillation to distill off the unreacted phenol, or by washing the crystalline matter with hot water to wash out the phenol.

The former method is preferred since the water treat-j ment results in wet phenol which should be tapped or dried before reuse. Also, some of the 2,2-bis(4-hydroxy-,

phenyl)propane may be lost due'to a slight solubility in water. The thermal decomposition of the crystalline complex is accomplished by heating complex under a reduced pressure of about 25-70 mm.

at about 100 C.-125 C. and then heating to 200 C.- periods of time to drive off last traces 220 C. for short of phenol. The 2,2-bis(4-hydroxyphenyl)pr0paue thus recovered is usually above 9597 percent pure.

of recovery of the product the crystalline I lized from dilute acetic, acid to further purify the product.

mixture is separated from the cold aqueous mixture and distilled to recover the 2,2-bis(oxyaryl)propane produced in the reaction as the still residue. Other recovery meth-,

ods will occur to those skilled in the art.

The following examples are illustrative.

Example 1 To 281.2 grams (3 moles) of reagent grade phenol which'had been topped to removed the water present, 7.3

grams (0.17m0le) of boron trifluoride was added at 50 C.' C. by bubbling the boron trifiuoride through the molten phenol until the desired weight of catalyst had been added, as determined by periodically weighing the reaction flask. Air was excluded 'in the reaction by.

sweeping the system for two minues with nitrogen, and 20.0 grams (0.5 'mole) of propadiene as a gas were slowly added below the liquid level of'the phenol-catalyst mixture. The reaction was maintained at 50'C.-55 C. during the 32 minutes that the propadiene was being added.

The product was recovered after the reaction was completed by adding 50 ml.'of cold water and 11.1 grams (0.2 mole) of calcium oxide to the reaction mixture and filtering the mixture at 50 C.55 C. to remove the inorganic matter. The water and unreacted phenol were removed from the washed reaction mixture by distilla tion at 10-15 mm. pressure and the pot residue consisted of nearly pure 2,2-bis(4-hydroxyphenyl)propane melting at 158 C. A yield of 85.9 percent of 2,2-bis (4-hydroxyphenyl) propane based on propadiene added was realized.

Example 2 To 324 grams maintained at 39 hydrous aluminum chloride was added with mixing and the system flushed with nitrogen'for two minutes. To

facilitate phase separations. 'washed successively with 'n' =1.692; elemental analysis; ported physical properties of this compoundare-r boiling this mixture 19.9 grams (0.50 'mole) of propadiene as a gas was slowly added below the surface of the liquid over a period of about .100 minutes while the temperature was maintained at 39 C.-47 C. On completion of the addition of the propadiene, the reaction mixture then was poured into a mixture of ice and 10 percent hydrochloric acid. A yellow layer rising to the top of the ice mixture was removed and diluted with 100 ml. of diethyl ether to The organic layer was ml. portions of 10 percent hydrochloric acid, water, 5 percent sodium hydroxide and twice more with water. from the washed material by distillation at 10 mm. pressure, and colorless 2,2-bis(4-methoxyphenyl) propane was obtained as the distillate by reducing the pressure in the still to 3 mm.

Yield of the 2,2-bis (4-methoxyphenyl) propane Was 43 percent based on=propadiene,

having the following properties: boiling point 183 G, 80.1; H, 8.2. Re-

(3.0 moles) of reagent grade anisole C., 13.5 grams (0.10 mole) of am.

Unreacted anisole was removed .trifluoride was added by bubbling through the .molten phenol until 1.4 grams (0.02mole) had been absorbed as determined by periodic weighing of the reaction flask after whichS grams (0.20 mole) rot propyne was .added :as :a gas below the liquid level of the mixture over .a periodtof .32 minutes while stirring. The reaction temperature was maintained at 50 C. during the addition.

At the termination of the addition of the propyne, the

reaction mixture was stirredfor an additional'45 minutes while cooling .to a temperature below 40 C. to cause "the phenol-2,2-bis (4-hydroxyphenyl)prop ane complex to crystallize in the .reaction mixture.

tifIfresh-inoltenidry1 at' 20 mm. pressureto drive off 7 The .crys'talswere tered ofi atiaboutA'l? C. and washed with 53.5 grams 1 enol. This crystalline complex was.

1th complex, and 24.5 grams of pure hen 1)prQpane were recovered from uhad a clear melting point "of moles) of redistilled 'orthocresol :at"

.30 ts a yield .of 54-55 percent of 'enynpropane 'Zb'ase'dpn propyna added"with sstirring' by bubbling the boron :trifluoride',

' through thel r'nolten 'cresol .until the desired weight of catalysthad been:

"dd 3 the system was purged with nitrogen. Then 43'.7:'grams. (-1.09 moles) of propadiene gas was slowlyadded withsstirring over a five hour period at apoint below the surface of the cresol-catalyst mixture, whilemaintainingthe temperature at 49 C.--

[55 .C. The reactionmixtu-re was stirredfor ,30 minutes after the addition of the .propadi'ene Was completed.

The product was recovered by ,decomposingthe catalyst with ,:ml. of Water and 10 grams (0.18 mole) of calcium oxide. After standingfor two days the inorganic precipitate was filtered off and 10 more grams of calcium oxide added. The unreacted o-cresol was removed :by distillation at .mm. pressure at a temperature of 1.82 C. The still residue was fractionally distilled at 1 mm. pressure and 151 grams of crude 2,2-bis(4-hydroxy- 3 methylphenyl)propane was collected between 187 C.- 1'94-61. This represents ayield of 54 percent. Crystals of pure 2,2-bis(4-hydroxy-3-methylphenyl)propane were obtainedfrom a benzene-n-hexane .solution after prolonged standing at about 2 C. This compound had a melting point of 99 C.-105 C., and an elemental analysis as follows: C, 79.49; H, 8.03; phenolic .OH, 12.66. Calculated analysis .for C17H2002 is C, 79.65; .H, 7.87.; phenolic 10H, 13.27. Previous reported melting points of 2,2-bis (4-hydroxy-3-methylphenyl1propane are not consistent, varying from 965 C. to 140 C.

Example 5 "To 280.0 grams (2.59 moles) ofreagent grade anisole, 1'1.7grams (.089 mole) of anhydrous aluminum chloride was added with stirring and the "system flushed with nitrogen. To this mixture 8.3 grams (.458 mole) of propyne as a gas was slowly added at a point below the surface of the liquid over a period of about 50 minutes, while the reaction temperature was maintained at 33 C.- 46 C. On completion of the addition of the propyne, 1m :reaction mixture was stirred for an additional :one

- pressure of 20 mm. Hg, recovering overlie .der of thejunreacted phenol,' -leaving 2,

.c ent.based on propadiene. f'Ehe'2,2-bisf( 4-h propane had.a meltingkpointot 15.6C. I I v iiThe phenol-catalyst"filtrate'and the "phenol'used :for

' percent of the weight of the phenol.

'6 half heur whijle cooling :to roomq-tenipcrature. wh reastion mixture was worked up in the usual mannerlby flecomposing the catalyst with cold water and washing with mlpportions of '10 percent HCI solution, 'water and dilute alkali. The unreacted :anisole was stripped off and the product, 2,2-bis,(4-methoxyphenyl)propane, @was isolated by distillation. A 30 percent yield :of product boiling at 176 C.178 C. at 2 mm. Hg pressure was isolated.

Example :6

To 141 grams (1.5 moles) of reagent grade phenol, which had been topped to remove any water presentflJS grams of boron trifiuoride'was added with stirring, and the system was'purged with nitrogen'for'l minutes. vAfter purging, ten grams .,(.'0.25mo1e') of propa'diene'wereislowly addedat apoint below the surface of the phenol catalyst mixture over a'period'of 14 minutes whil'eithetemperature was maintainedat 50 C.-,S5 C. 'Thereaction mixture was permitted to cool to room temperature :and copious crystallization occurred. A

The reaction mixture was heated'to 41 C.-42 C. and filtered at that temperature,;saving both the solid crystalline material and'the filtrate which contained .unreacted phenol and part of the catalyst. The sold' phenol-bis- "phenol complex was washed with fresh" to remove the last of the adhering lboron trifi oridecatalyst. The crystalline matter was distilled phenol) propane as the still residue. *Yi

washing thelcrystalline complex -were "combined and addi- .Itional phenol added so that 'the're wasagainapproximately "1.5 moles-of phenol and the catalystagain comprised .11 T .tliis'phenolcatalyst mixture, at a temperatu'reof 50 Ci-55 C.,' 10

grams f pr'opa'diene (0-L25'mole'ywashlowly added over a period of- 42 minutes. 'Produetgrefcovery was the same as in the first part, and yield ,onthis recycle run of 2,2 t:

bis(4-hydroxyphenyl)propane was 76 percent based on propadiene. The product had .'a melting .point of C.

This run showsthat the process-"can be continuous or semi-continuous, utilizing the .frecycle phenol and catalyst.

Example 7 '1' T0141 grams-($1.5 moles) of'phenol there was slowly added 1.4 grarns (l percent) of:boronxtrifluorideasthe acidic condensing agent. The mixture was maintained at 50 C.-5.5 C. while a gaseousmixture of propyne (33.7 mole percent) and propadiene (i65.l-mole percent) was slowly introduced below the surface of the liquid phenol-catalyst mixture over a period of one hour and twenty minutes. Upon the completion of .the reaction, the product was isolated as described in Example .6. The 2,2-bis(4-hydroxyphenyl)propane, isolated as a potresidue, had a good color and a melting point of 153 C.

Example 8 To 62.9 grams (0.51 mole) of ortho-methyl anisole, there was added 6.8 grams (0..051 mole) of anhydrous aluminum chloride as the condensing agent. .Themixture was maintained at "50 C.55 .C. as propyne gas was slowly introduced 'into the reaction mixture beneath the surface ofthe liquid. The procedure'of'Example 2-was followed to remove the aluminum chloride, and the remaining mixture stripped at 50 mm. Hg pressure to recover the unreacted ortho-methylanisole. v Ayicld of 54 percent of 2,2-bis( 4 methoxy-3-methylphenyl)propane was recovered.

The product was very viscous, having an elemental analysis as follows: Carbon 80.24%; hydrogen, 8.52%; oxygen (by difference), 11.24%. Calculated analysis for 2,2-bis(4-methoxy-3-methylphenyl)propane is as follows;

eral formula I claim::-..-.' I v 1. A process for producing a 2,2-bis(oxyaryl)propane which comprises admixing and reacting an acyclic C H hydrocarbon with an oxyaryl compound having the gen wherein R and R? are selected from the groupv consisting of hydrogen'and lo'weralkyl groups in the. presence of an.acidicjcondensatioh. agent selectedffrom the group vtio'tisisting of the. 'Friedel-Crafts catalysts and sulfuric acid,.'phei1ol acid, and hydrogen-fluoride,Iwiththe proviso that 'whclirIR and R? are'hyd'rogens,"jaluminum'chloride is. excluded as the acidic'condensing'agent, at a temperature within the. 'range'ofabout .C. to about 100 C., said oxyar'yl compound beingpres'ent in molar amounts" of at least two molesper mole of saidfC H hydrocarbon.

2. The process for producing a,2,2-bis(oxyaryl)propane which comprises admixing and reactingpropadiene with an oxyaryl' compound having the general formula wherein R and R are members selected from the group.

consisting of hydrogen" and lower alkyl groups in the presence of an acidic condensation agent selected from the group consisting 'of the. Friedel-Crafts catalysts and sulfuric acid, phenol sulfonic acid, and hydrogen fluoride, with the proviso tha't when R and R arehydrogens, aluminum chloride is excluded as the acidic condensing agent, at a temperature within the range of about 0 C. to-about 100 C.'

-4. The process for producing 2,2-bis(oxyaryl)propane which comprises admixing and reacting an acyclic C H hydrocarbon with an oxyaryl compound having the general formula wherein R and R are members. selected from the group consisting. of hydrogen and lower alkyl groups in the presence of a Friedel-Crafts catalyst, with the proviso that ,when R and R are hydrogens, aluminum chloride is excluded, ata temperature between about. 0 C. and about 100 C.

.- 5. The processfor producing 2,2-bis(oxyaryl)propane which comprises reacting a mixture of an acyclic C H hydrocarbon with. an oxyaryl compound having the gen eral formula wherein R and R are members selected from the group consisting of hydrogen and lower alkyl group's said reactants being present in amounts of at least two moles of the oxyaryl compound per mole of C H hydrocarbons, in the presence of boron trifluoride at a temperature of from about 0 C. to about C. I 6. A process for the production of 2,2-bis(4-hydro'xyphenyl)propane which comprises admixing and reacting phenol with an acyclic C l-I hydrocarbon in the presence of an acidic condensing agent selected from the group c'o'nsisting'of Friedel-Crafts catalysts and sulfuric acid, phenol-sulfonic-acidand hydrogen fluoride, with the proviso that aluminum chloride is excluded as the acidic condensing agent at a temperature within the range of about 0 C. to about 100' CL d 7. A proizessactzording to claim 6 wherein the G l-I hydrocarbon isprop'adiene.

8. processaccording to claim 6 wherein the hydrocarbon is propyne.

9. A process according to claim 6 wherein the C li;

11. A process accordingto claim 10 wherein the C l-I;

hydrocarbon is propadiene.

12. A process according to claim 10 wherein the C H hydrocarbon is propyne. 1

13. A process according to claim 10 wherein the C 131; hydrocarbon is a mixture of propadiene and propyn e.

14. A process for the production of 2,2-bis(4-hydroxyphenyl) propane which includes the steps of heating a mixture of phenol and an acidic condensing agent selected from the group consisting of Friedel-Crafts catalysts and sulfuric acid, phenol sulfonic acid and hydrogen fluoride, with the proviso that aluminum chloride is excluded as the acidic'condensing agent to a temperature within the range from about 40 C. to about 100 C. and adding an acyclic C H hydrocarbon, and thereafter recovering the 2,2-bis(4-hydroxyphenyl)propane' thus produced.

15. A process for the production of 2,2-bis(4-methoxyphenol)propane which includes the steps of slowly bub-' bling an acyclic C H hydrocarbon through a mixture of anisole and an acidic condensing agent selected from the group consisting of Friedel-Crafts catalysts and sulfuric acid, phenol sulfonic acid and hydrogen fluoride, at a temperature of between about 0 C. and about 100 C., and thereafter recovering the 2,2-bis(4-methoxyphenyl) propane thus produced.

16. A process for the production of 2,2-bis(4-hydroxy- 3-methylpheny1)propane which includes the steps of slowly bubbling a C -H hydrocarbon through a mixture of ortho-cresol and an acidic condensing agent selectedfrom the group consisting of Friedel-Crafts catalysts and sulfuric acid, phenol sulfonic acid and hydrogen fluoride, at a temperature of between about 0" C. arid about 100 C., and thereafter recoveringlthe 2-,2-bis(4-' hydroxy-3-methylphenyl)propane thus produced.

17. A process for the production of 2,2-bis(4-rnethoxy- 3-methylphenyl)propane which includes the steps of slowly bubbling an acyclic C H hydrocarbon through a mixture of ortho-methyl anisole and an acidic condensing agent selected from the group consisting of Friedel-Crafts catalysts and sulfuric acid, phenol sulfonic acid and hy-f drogen fluoride, at a temperature of between about 0 C.

and about 100 C., and thereafter recovering the 2,2-bis (4-methoxy-3-methylphenyl) propane thus produced.

18. .A process for producing a 2,2-bis(oxyaryl)propanewhich includes the steps of admixing and reacting propyne with an oxyaryl compound having the general formula wherein R and R are members selected from the group consisting of hydrogen and lower alkyl groups in the presence of a Friedel-Crafts catalyst, with the proviso that when R and R are hydrogens, aluminum chloride is excluded, at a temperature between about 30 C. and about 60 C.

19. A process for the production of 2,2-bis(4-hydroxyphenyl)propane which includes the steps of admixing and reacting propyne and phenol in the presence of a Friedel- Crafts catalyst excepting aluminum chloride at a temperature between about 30 C. and about 60 C.

20. A process for the production of 2,2-bis(4-hydroxyphenyl)propane which includes the steps of slowly bubbling an acyclic C H hydrocarbon gas through a mixture of phenol and boron trifluoride maintained at a tempera- 10 ture of between about 0 C. and about 100 C., and recovering the 2,2-bis(4-hydroxyphenyl)propane thus produced.

21. A process for the production of 2,2-bis(4-hydroxypheny1)propane which includes the steps of heating a mixture of phenol and boron trifiuoride to a temperature within the range from about C. to about C. and adding an acyclic C 11 hydrocarbon, and thereafter recovering the 2,2-bis(4-hydroxyphenyl)propane thus produced.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Royals: Advanced Organic Chemistry, 1954, p. 380.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent 4,4 April 28, 1959 Joseph P. Henry It is hereby certifiedthat error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should readas corrected below.

Column 4, line 28, for "removed" reed remove column '7, line 16, after "phenol" insert sulfonic Signed and sealed this 15th day of December 1959.

(SEAL) Attest:

KARL WINE ROBERT c. WATSON Attesting Ofiicer Commissioner of Patents 

1. A PROCESS FOR PRODUCING A 2,2-BIS(OXYARY)PROPANE WHICH COMPRISES ADMIXING AND REACTING AN ACYCLIC C3H4 HYDROCARBON WITH AN OXYARYL COMPOUND HAVING THE GENERAL FORMULA 